Functionalized N-substituted pyrrolidonium ionic liquids

ABSTRACT

This invention relates to compounds useful as ionic liquids that are based on an N-substituted pyrrolidinone and incorporate a pendant ammonium cation that is spaced from the pyrrolidone ring by a variable length linker.

TECHNICAL FIELD

This invention relates to N-substituted pyrrolidonium compounds that areuseful as ionic liquids.

BACKGROUND

Ionic liquids are liquids composed of ions that are fluid at or belowabout 100° C. Ionic liquids exhibit negligible vapor pressure, and withincreasing regulatory pressure to limit the use of traditionalindustrial solvents due to environmental considerations such as volatileemissions and aquifer and drinking water contamination, much researchhas been devoted to designing ionic liquids that could function asreplacements for conventional solvents.

Ionic liquids typically consist of a salt of an organic cation such asthe N-alkylpyridinium, 1,3-dialkylimidazolium, tetraalkylammonium,tetraalkylphosphonium or trialkylsulfonium cation. U.S. Pat. No.7,157,588 describes, for example, ionic liquids based on N-substitutedpyrrolidones, which have a pendant ammonium cation that is spaced fromthe pyrrolidone ring by a variable length linker. A need remains,however, for other ionic liquids that may be designed for use inselected applications, particularly those that may be prepared at leastin part from renewable resources.

SUMMARY

This invention provides a compound represented by the structure of thefollowing Formula 1:

wherein

(a) Z is —(CH₂)_(n)—, wherein n is an integer from 2 to 12;

(b) R² are R³ are each independently H or a C₁ to C₆ straight-chain orbranched alkyl group;

(c) R⁴ is —[(CH₂)_(p)—X]_(q)—(CH₂)_(r)—Y—R⁶ wherein X and Y are eachindependently O or N, r and p are each independently an integer from 1to 4, q is an integer from 0 to 8, and R⁶ is H or a C₁ to C₆straight-chain or branched alkyl group; and

(d) A⁻ is an anion selected from the group consisting of levulinate,[BF₄]⁻, [PF₆]⁻, [SbF₆]⁻, [CH₃CO₂]⁻, [HSO₄]⁻, [CF₃SO₃]⁻, [HCF₂CF₂SO₃]⁻,[CF₃HFCCF₂SO₃]⁻, [CF₃—O—CFHCF₂SO₃]⁻, [CF₃CF₂OCFHCF₂SO₃]⁻,[CF₃CF₂CF₂OCFHCF₂SO₃]⁻, [HCClFCF₂SO₃]⁻, [(CF₃SO₂)₂N]⁻, [AlCl₄]⁻,[CF₃CO₂]⁻, [NO₃]⁻, [SO₄]²⁻, Cl⁻, Br⁻, I⁻, and F⁻.

DETAILED DESCRIPTION

This invention relates to compounds that are derived, in part, fromN-substituted pyrrolidones. These compounds include an anion, and acation in which there is a pendant ammonium cation spaced from apyrrolidone ring by a variable length linker. This linker is denominatedZ in the description of Formula I as set forth herein. These compoundsare useful as ionic liquids, and can be used for example as a solvent,as a catalyst for various kinds of reactions (such as an alkylationreaction), and as an absorbent for various gases (such as CO₂). Thesecompounds also have the advantage that the cationic portion, and some ofthe associated anions, may be readily prepared from levulinic acid, orlevulinic acid derivatives, which may be obtained from the hydrolysis ofinexpensive renewable biomass feedstocks.

In the description of the compositions hereof, the followingdefinitional structure is provided for certain terminology as employedvariously in the specification:

An “alkyl” group is a monovalent (i.e. having a valence of one) grouphaving the general Formula C_(n)H_(2n+1).

“Biomass” refers to any cellulosic or lignocellulosic material, andincludes materials containing cellulose, and optionally further includeshemicellulose, lignin, starch, oligosaccharides and/or monosaccharides.Biomass may also include additional components such as proteins and/orlipids. Biomass suitable for use herein may be derived from a singlesource, or may be a mixture derived from more than one source. Suchsources include without limitation bioenergy crops, agriculturalresidues, municipal solid waste, industrial solid waste, sludge frompaper manufacture, yard waste, wood and forestry waste. Examples ofbiomass include without limitation corn grain, corn cobs, crop residuessuch as corn husks, corn stover, grasses, wheat, wheat straw, hay, ricestraw, switchgrass, waste paper, sugar cane bagasse, sorghum, soy,residue from the milling of grain, trees, branches, roots, leaves, woodchips, sawdust, shrubs and bushes, vegetables, fruits, flowers andanimal manure.

A “catalyst” is a substance that affects the rate of a reaction but notthe reaction equilibrium, and emerges from the reaction chemicallyunchanged.

“Conversion” refers to the weight percent of a particular reactant thatis converted in a reaction to product.

A “hydrocarbyl” group is a monovalent group containing only carbon andhydrogen.

An “ionic liquid” is an organic salts that is fluid at or below about100° C.

A “levulinate” ion is an anion represented by the structure of thefollowing formula:

A “metal catalyst” is a catalyst that includes at least one metal, atleast one Raney® metal, compounds thereof or combinations thereof. Asupported metal catalyst is a supported catalyst in which the catalystagent is a metal.

A “metal promoter” is a metallic compound that is added to a catalyst toenhance the physical or chemical function thereof in a reaction. A metalpromoter can also be added to retard undesirable side reactions and/oraffect the rate of the reaction.

A “promoter” is an element of the periodic table that is added to acatalyst to enhance the physical or chemical function thereof in areaction. A promoter can also be added to retard undesirable sidereactions and/or affect the rate of the reaction.

“Pyrrolidinone” is used synonymously with the term “pyrrolidone”;“pyrrolidin-2-one” is used synonymously with the term “2-pyrrolidone”.

“Selectivity” refers to the weight percent of a particular reactionproduct in the total weight of the product of a reaction (including theweight of unreacted reactants).

This invention provides compounds represented by the structure of thefollowing Formula 1:

wherein (a) Z is —(CH₂)_(n)—, wherein n is an integer from 2 to 12; (b)R² are R³ are each independently H or a C₁ to C₆ straight-chain orbranched alkyl group; (c) R⁴ is —[(CH₂)_(p)—X]_(q)—(CH₂)_(r)—Y—R⁶wherein X and Y are each independently O or N, r and p are eachindependently an integer from 1 to 4, q is an integer from 0 to 8, andR⁶ is H or a C₁ to C₆ straight-chain or branched alkyl group; and (d) A⁻is an anion selected from the group consisting of levulinate, [BF₄]⁻,[PF₆]⁻, [SbF₆]⁻, [CH₃CO₂]⁻, [HSO₄]⁻, [CF₃SO₃]⁻, [HCF₂CF₂SO₃]⁻,[CF₃HFCCF₂SO₃]⁻, [CF₃—O—CFHCF₂SO₃]⁻, [CF₃CF₂OCFHCF₂SO₃]⁻,[CF₃CF₂CF₂OCFHCF₂SO₃]⁻, [HCClFCF₂SO₃]⁻, [(CF₃SO₂)₂N]⁻, [AlCl₄]⁻,[CF₃CO₂]⁻, [NO₃]⁻, [SO₄]²⁻, Cl⁻, Br⁻, I⁻, and F⁻.

In various embodiments, n in Z may be an integer from 2 to 6, and isfrequently 2. In other embodiments, R² and R³ may each independently beH, —CH₃, —CH₂CH₃ or —CH₂CH₂CH₃, and frequently R² is —CH₃ and R³ is—CH₂CH₂CH₃. In other embodiments, r and p are 2 to 4, more typically 2.In another embodiment q is 0 to 4, more typically 0. In otherembodiments, X and Y are both 0, or X and Y are both N, more typically Yis O. In other embodiments, R⁶ is H, R² and R³ are —CH₃, R⁴ is—(CH₂)₂—O—(C₂H₅), —(CH₂)₂—O—(CH₃) or —(CH₂)₂—OH, and A⁻ is levulinate,[CF₃HFCCF₂SO₃]⁻ or [(CF₃SO₂)₂N]⁻.

A compound hereof may be synthesized from a pyrrolidin-2-one asrepresented by the structure of the following Formula 2, wherein Z, R²and R³ are as defined above.

Synthesis of an N-hydrocarbyl pyrrolidin-2-one

The pyrrolidin-2-one may be synthesized by contacting levulinic acid, oran ester thereof, with a diamine of the Formula R²R³N—Z—NH₂ in thepresence of hydrogen gas and a catalyst according to Reaction (I):

wherein Z, R² and R³ are as defined above, and R⁵ is H, —CH₃, —CH₂CH₃,or a C₃ to C₈ straight-chain or branched alkyl group. In anotherembodiment, the pyrrolidin-2-one may be synthesized by contacting a saltof levulinic acid, such as ammonium levulinate, with a diamine of theFormula R²R³N—Z—NH₂ in the presence of hydrogen gas and a catalyst. Invarious embodiments, in a diamine suitable for use herein, Z may be—(CH₂)_(n)— wherein n is an integer from 2 to 12, and R² and R³ may eachindependently be H, —CH₃, —CH₂CH₃ or a C₃ to C₆ straight-chain orbranched alkyl group.

The pyrrolidin-2-one formed in Reaction (I) can be synthesized accordingto methods and conditions as taught in or adapted from U.S. Pat. Nos.6,818,593 or 6,900,337, each of which is by this reference incorporatedin its entirety as a part hereof for all purposes. For the synthesis ofa pyrrolidin-2-one according to Reaction (I), a molar ratio of diamineto levulinic acid, or a salt or ester thereof, at the start of thereaction may be about 0.01/1 to about 100/1, or about 0.3/1 to about5/1. The temperature range for this reductive amination reaction may befrom about 25° C. to about 300° C., or about 75° C. to about 200° C. Thepressure may be in the range of from about 0.3 MPa to about 20.0 MPa, orfrom about 1.3 MPa to about 7.6 MPa. The reaction may be performed in anon-reacting solvent medium such as water or an alcohol, ether orpyrrolidone. Alternatively, an excess of diamine can also act as areaction medium.

The principal component of a catalyst suitable for use in Reaction (I)may be selected from metals from the group consisting of palladium,ruthenium, rhenium, rhodium, iridium, platinum, nickel, cobalt, copper,iron, osmium; compounds thereof; and combinations thereof. A chemicalpromoter may augment the activity of the catalyst. The promoter may beincorporated into the catalyst during any step in the chemicalprocessing of the catalyst constituent. Suitable promoters for thisprocess include metals selected from tin, zinc, copper, gold, silver,and combinations thereof. The preferred metal promoter is tin. Otherpromoters that can be used are elements selected from Group 1 and Group2 of the Periodic Table.

The catalyst may be supported or unsupported. A supported catalyst isone in which the active catalyst agent is deposited on a supportmaterial by a number of methods such as spraying, soaking or physicalmixing, followed by drying, calcination and if necessary, activationthrough methods such as reduction or oxidation. Materials frequentlyused as a support are porous solids with high total surface areas(external and internal) that can provide high concentrations of activesites per unit weight of catalyst. A catalyst support may enhance thefunction of the catalyst agent.

The catalyst support useful herein can be any solid, inert substanceincluding without limitation oxides such as silica, alumina and titania;barium sulfate; calcium carbonate; and carbons. The catalyst support canbe in the form of powder, granules, pellets, or the like. A preferredsupport material is selected from the group consisting of carbon,alumina, silica, silica-alumina, silica-titania, titania,titania-alumina, barium sulfate, calcium carbonate, strontium carbonate,compounds thereof and combinations thereof. Supported metal catalystscan also have supporting materials made from one or more compounds. Morepreferred supports are carbon, titania and alumina. Further preferredsupports are carbons with a surface area greater than 100 m²/g. Afurther preferred support is carbon with a surface area greater than 200m²/g. Preferably, the carbon has an ash content that is less than 5% byweight of the catalyst support, where the ash content is the inorganicresidue (expressed as a percentage of the original weight of the carbon)which remains after incineration of the carbon.

The preferred content of a metal catalyst in a supported catalyst isfrom about 0.1 wt % to about 20 wt % of the supported catalyst based onmetal catalyst weight plus the support weight. A more preferred metalcatalyst content range is from about 1 wt % to about 10 wt % of thesupported catalyst. Combinations of metal catalyst and support mayinclude any one of the metals referred to herein with any of thesupports referred to herein. Preferred combinations of metal catalystand support include palladium on carbon, palladium on calcium carbonate,palladium on barium sulfate, palladium on alumina, palladium on titania,platinum on carbon, platinum on alumina, platinum on silica, iridium onsilica, iridium on carbon, iridium on alumina, rhodium on carbon,rhodium on silica, rhodium on alumina, nickel on carbon, nickel onalumina, nickel on silica, rhenium on carbon, rhenium on silica, rheniumon alumina, ruthenium on carbon, ruthenium on alumina and ruthenium onsilica. Further preferred combinations of metal catalyst and supportinclude palladium on carbon, palladium on alumina, palladium on titania,platinum on carbon, platinum on alumina, rhodium on carbon, rhodium onalumina, ruthenium on carbon and ruthenium on alumina.

A catalyst that is not supported on a catalyst support material is anunsupported catalyst. An unsupported catalyst may be platinum black or aRaney® (W.R. Grace & Co., Columbia Md.) catalyst. Raney® catalysts havea high surface area as a result of preparation by the selective leachingof an alloy containing the active metal(s) and a leachable metal(usually aluminum). Raney® catalysts have high activity due to thehigher specific area and allow the use of lower temperatures inhydrogenation reactions. The active metals of Raney® catalysts includenickel, copper, cobalt, iron, rhodium, ruthenium, rhenium, osmium,iridium, platinum, palladium; compounds thereof; and combinationsthereof. Promoter metals may also be added to the base Raney® metals toaffect selectivity and/or activity of the Raney® catalyst. Promotermetals for Raney® catalysts may be selected from transition metals fromGroups IIIA through VIIIA, IB and IIB of the Periodic Table of theElements. Examples of promoter metals include chromium, molybdenum,platinum, rhodium, ruthenium, osmium and palladium, typically at about2% by weight of the weight of the total metal.

Levulinic acid for use herein may be obtained from biomass. For theconversion of biomass to levulinic acid, biomass may be contacted withwater and an acid catalyst in a train of one or more reactors,preferably under pressure at elevated temperature. This basic process isdescribed, for example, in U.S. Pat. Nos. 5,608,105, 5,859,263,6,054,611 and 7,153,996, each of which is by this reference incorporatedin its entirety as a part hereof for all purposes. Generally, cellulosein the biomass is converted to levulinic acid and formate in one or morereactors. Levulinic acid produced from biomass may also be converted tolevulinic acid esters for example as described in U.S. Pat. No.7,153,996 through the reaction of levulinic acid with olefins.

Suitable diamines for use in Reaction (I) may, for example, be obtainedcommercially from suppliers such as Huntsman (Houston Tex.) or BASF(Mount Olive N.J.), or may be synthesized by methods such as thosediscussed in Eller and Henkes, Diamines and Polyamines [in Chapter 8 ofUllmanns Encyclopedia of Industrial Chemistry (2002), Wiley-VCH VerlagGmbH & Co.], or Chapter 22 in Experimental Methods in Organic Chemistry,3^(rd) Edition [Moore, Dalrymple and Rodig (Eds.), (1982) SaundersCollege Publishing, NY].

The formation of a pyrrolidin-2-one may be carried out in batch,sequential batch (i.e. a series of batch reactors) or in continuous modein equipment such as that discussed in Fogler, Elementary ChemicalReaction Engineering, 2^(nd) Edition [(1992), Prentice-Hall, Inc., N.J.,USA]. A pyrrolidin-2-one synthesized according to Reaction (I) may berecovered, for example, by distillation, or by filtration to removesolid acid catalyst particles, if present.

Conversion of the N-hydrocarbyl pyrrolidin-2-one

A compound hereof may be synthesized by quaternizing the non-ringnitrogen of the pyrrolidin-2-one to obtain a quaternary ammoniumcompound as represented by the structure of the following Formula 3:

wherein Z, R², R³ and R⁴ are each as defined above, and A′⁻ is selectedfrom the group consisting of Cl⁻, Br⁻ and I⁻.

To form a quaternary ammonium compound as described above, thepyrrolidin-2-one is contacted with an alkylating halide having theFormula R⁴-A wherein R⁴ is as described above, and A′⁻ is selected fromthe group consisting of Cl⁻, Br⁻ and I⁻. Compounds of the formula R⁴-A′can be obtained commercially, or can be prepared by methods such asthose discussed in U.S. Pat. Nos. 2,913,496, 4,820,672 or 6,136,586;Cardoso et al, J. Polymer Sci., Part B: Polymer Physics (1997), 35(3),479-488; or Lermit et al, J. of the Chem. Soc. (1947), 530-3.

The quaternization reaction may be carried out in an inert solvent suchas acetonitrile, acetone or dichloromethane. The quaternization may beaccomplished by refluxing of the reactants, optionally under an inertatmosphere. When the reactants are hygroscopic, it is preferable tocarry out the quaternization reaction, and/or the anion exchangereaction described below, under conditions that exclude water and air.The alkylating halide is present in slight excess (e.g. about 5 wt %excess) at the start of the reaction. The reaction may be carried out ata temperature in the range of from about 10° C. to about 100° C.; or inthe range of from about 30° C. to about 90° C.; or in the range of fromabout 60° C. to about 90° C. The time for the reaction is generally fromabout 1 minute to about 72 hours, or about 30 minutes to about 24 hours.Methods for performing quaternization reactions suitable for use forsuch purpose are further discussed in sources such as Organic Chemistry[Morrison and Boyd (ed.) 3^(rd) Edition (1973); Allyn and Bacon, Inc.,Boston; Chapter 23.5, pages 752-753].

Anion Exchange

The quaternary ammonium compound thus formed is next contacted withM⁺A⁻, wherein M is selected from the group consisting of H, Li, K, Na,Ag, Mg, Ca, Ce, Ba, Rb and Sr, and A⁻ is an anion selected from thegroup consisting of [BF₄]⁻, [PF₆]⁻, [SbF₆]⁻, [CH₃CO₂]⁻, [HSO₄]⁻, [NO₃]⁻,[CF₃SO₃]⁻, [HCF₂CF₂SO₃]⁻, [CF₃—O—CFHCF₂SO₃]⁻, [CF₃CF₂OCFHCF₂SO₃]⁻,[CF₃CF₂CF₂OCFHCF₂SO₃]⁻, [CF₃HFCCF₂SO₃]⁻, [HCClFCF₂SO₃]⁻, [(CF₃SO₂)₂N]⁻,[AlCl₄]⁻, [CF₃CO₂]⁻, [NO₃]⁻, [SO₄]²⁻, Cl⁻, Br⁻, I⁻ F⁻ and levulinate, toform a compound hereof according to the choice of anion desired. Priorto the exchange reaction, excess alkylating agent may be removed, forexample, by evaporation. In addition, the quaternary ammonium compoundmay be washed with a solvent and dried prior to anion exchange.

The anion exchange reaction may be carried out by mixing the quaternaryammonium compound with M⁺A⁻, optionally under an inert atmosphere. Theanion exchange reaction may be carried out at a temperature in the rangeof from about −20 C to about 100° C. for a time of about 1 second toabout 72 hours. Solvents useful in the reaction should be inert to thereactants and products, and include, for example, methanol, ethanol,acetone and/or acetonitrile. Choice of the solvent or mixture thereofwill facilitate separation of the compound containing the desired anionfrom the remainder of the reaction mixture. Additional techniques thatmay enhance the anion exchange reaction include as ultrasonication asdiscussed in WO 03/048078.

Fluoroalkyl sulfonate anions suitable for used in the anion exchangereaction may be synthesized from perfluorinated terminal olefins orperfluorinated vinyl ethers generally according to the methods discussedin Koshar et al [J. Am. Chem. Soc. (1953) 75:4595-4596], U.S. Ser. No.06/276,670 and U.S. Ser. No. 06/276,671. In one embodiment, sulfite andbisulfite are used as a buffer in place of bisulfite and borax, and inanother embodiment, the reaction is carried out in the absence of aradical initiator. The product of the anion exchange reaction may berecovered by a technique such as evaporation of the reaction solventunder reduced pressure, decantation and/or filtration to removeprecipitated salts.

1,1,2,2-Tetrafluoroethanesulfonate,1,1,2,3,3,3-hexafluoropropanesulfonate,1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate, and1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate may be synthesizedaccording to a modifications of Koshar in which

a mixture of sulfite and bisulfite is used as the buffer, and freezedrying or spray drying isolates the crude1,1,2,2-tetrafluoroethanesulfonate and1,1,2,3,3,3-hexafluoropropanesulfonate products from the aqueousreaction mixture,

acetone is used to extract the crude 1,1,2,2-tetrafluoroethanesulfonateand 1,1,2,3,3,3-hexafluoropropanesulfonate salts; and

1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate and1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate are crystallizedfrom the reaction mixture by cooling.

Each of the formulae shown herein describes each and all of theseparate, individual compounds that can be assembled in that formula by(1) selection from within the prescribed range for one of the variableradicals, substituents or numerical coefficients while all of the othervariable radicals, substituents or numerical coefficients are heldconstant, and (2) performing in turn the same selection from within theprescribed range for each of the other variable radicals, substituentsor numerical coefficients with the others being held constant. Inaddition to a selection made within the prescribed range for any of thevariable radicals, substituents or numerical coefficients of only one ofthe members of the group described by the range, a plurality ofcompounds may be described by selecting more than one but less than allof the members of the whole group of radicals, substituents or numericalcoefficients. When the selection made within the prescribed range forany of the variable radicals, substituents or numerical coefficients isa subgroup containing (i) only one of the members of the whole groupdescribed by the range, or (ii) more than one but less than all of themembers of the whole group, the selected member(s) are selected byomitting those member(s) of the whole group that are not selected toform the subgroup. The compound, or plurality of compounds, may in suchevent be characterized by a definition of one or more of the variableradicals, substituents or numerical coefficients that refers to thewhole group of the prescribed range for that variable but where themember(s) omitted to form the subgroup are absent from the whole group.

In various embodiments of this invention, an ionic liquid may be formedby selecting any of the individual cations described or disclosedherein, and by selecting to pair therewith any of the individual anionsdescribed or disclosed herein, and the ionic liquid(s) thus formed maybe used for any of the purposes disclosed herein such as carbon dioxideabsorption. Correspondingly, in yet other embodiments, a subgroup ofionic liquids may be formed by selecting a subgroup of any size ofcations, taken from the total group of cations described and disclosedherein in all the various different combinations of the individualmembers of that total group, and pairing therewith a subgroup of anysize of anions, taken from the total group of anions described anddisclosed herein in all the various different combinations of theindividual members of that total group. In forming an ionic liquid, or asubgroup of ionic liquids, by making selections as aforesaid, the ionicliquid or subgroup will be formed in the absence of the members of thegroup of cations and/or anions that are omitted from the total groupthereof to make the selection, and, if desirable, the selection may thusbe made in terms of the members of the total group that are omitted fromuse rather than the members of the group that are included for use.

The compounds hereof are useful as ionic liquids, and are in generalfluid at or below a temperatures of about 100° C. The physical andchemical properties of an ionic liquid are influenced by the choice ofcation. For example, increasing the chain length of one or more of thealkyl chains of the cation will affect properties such as the meltingpoint, hydrophilicity/lipophilicity, density, viscosity, and solvationstrength of the ionic liquid. Effects of the choice of cation and anionon the physical and chemical properties of an ionic liquid are furtherdiscussed in sources such as Wasserscheid and Keim [Angew. Chem. Int.Ed., 39, 3772-3789 (2000)] and Sheldon [Chem. Commun., 2399-2407(2001)]. The compounds hereof may be utilized in one-phase systems ormultiple-phase systems as a solvent, as a catalyst for various kinds ofreactions (such as an alkylation reaction), and as an absorbent forvarious gases (such as CO₂).

Other related N-substituted pyrrolidonium compounds, and methods forusing same for carbon dioxide absorption, are disclosed in theconcurrently-filed, commonly-assigned applications listed as follows byattorney docket number and title, each of which is by this referenceincorporated in its entirety as a part hereof for all purposes, to-wit:

-   -   (N-Substituted Pyrrolidonium Ionic Liquids), now U.S.        application Ser. No. 12/328,057;    -   (N-Substituted Pyrrolidonium Ionic Liquids with Expanded        Linker), now U.S. Provisional Application No. 61/119,781; and    -   (Carbon Dioxide Removal and Ionic Liquid Compounds Useful        Therein), now U.S. Provisional Application No. 61/119,783.

EXAMPLES

Compounds provided by this invention, and the advantageous attributesand effects thereof, may be seen in a series of examples as describedbelow. The embodiments of this invention on which the examples are basedare representative only, and the selection of those embodiments toillustrate the invention does not indicate that materials, componentsand reactants, and/or conditions, protocols and regimes, not describedin these examples are not suitable for practicing this invention, orthat subject matter not described in these examples is excluded from thescope of the appended claims and equivalents thereof.

In the examples, the following abbreviations are used: nuclear magneticresonance is abbreviated NMR; thermogravimetric analysis is abbreviatedTGA; gas chromatography is abbreviated GC; gas chromatography-massspectrometry is abbreviated GC-MS; thin layer chromatography isabbreviated TLC; centigrade is abbreviated C; mega Pascal is abbreviatedMPa; gram is abbreviated “g”; milliliter is abbreviated “mL”; hour isabbreviated “hr”.

Materials.

The following materials were used in the examples. The commercialreagents and solvents acetonitrile (CAS Registry No. 75-05-8, 99.8%purity), 2-chloroethanol (CAS Registry No. 107-07-3, 99% purity),dichloromethane (CAS Registry No. 75-09-2, 99.5% purity), diethyl ether(CAS Registry No. 60-29-7, 99% purity), 2-chloroethyl ethyl ether (CASRegistry No. 628-34-2, 98% purity, Fluka product),

2-chloroethyl methyl ether (CAS Registry No. 627-42-9, 98% purity),

ethyl levulinate (CAS Registry No. 539-88-8, 99% purity), ethyl acetate(CAS Registry No. 141-78-6, 99.8% purity), levulinic acid (CAS RegistryNo. 123-76-2, 98% purity), silver (I) oxide (CAS Registry No.20667-12-3, 99% purity), bis(trifluoromethane)sulfonimide (CAS RegistryNo 82113-65-3, 97% purity, Fluka product), andN,N-dimethylethylenediamine (CAS Registry No. 108-00-9, 98.0% purity,Fluka product)were obtained from Sigma-Aldrich Chemical Company (Milwaukee, Wis., USA)and used as received without further purification.

Potassium hexafluoropropanesulfonate (CAS Registry No. 905298-79-5, 95+%purity) was prepared according to the methods disclosed in US patentSer. No. 06/276,671. ESCAT® 142 catalyst (5 wt % palladium on activatedcarbon) was obtained from Engelhard (now BASF Catalysts, Iselin N.J.).

Example 1 illustrates a method for the preparation of the1-(2-(dimethylamino)ethyl)-5-methylpyrrolidin-2-one (MeDMAP)intermediate used in the subsequent preparation of various exemplaryionic liquids. Examples 2-6 describe the preparation of severalexemplary ionic liquids representative of a class of compounds that arebased on this MeDMAP intermediate.

Example 1 Synthesis of1-(2-(dimethylamino)ethyl)-5-methylpyrrolidin-2-one (MeDMAP)

1-(2-(dimethylamino)ethyl)-5-methylpyrrolidin-2-one (MeDMAP), C₉H₁₈N₂O,with a molecular weight of 170.25 g mol⁻¹ and structure as shown inFormula 4:

was prepared as described below via the cyclic reductive amination ofethyl levulinate with N,N-dimethylethylenediamine (and as described inU.S. Pat. No. 7,157,588):

To a 600-mL Hastelloy® C-276 autoclave reactor (Parr Model 2302 HC)equipped with a gas entrainment turbine impellor and electrical heatingmantle was added 150.0 g (1.04 mol) ethyl levulinate, 192.6 g (2.18 mol)N,N-dimethylethylenediamine, and 7.5 g ESCAT® 142 5% Pd/C catalyst. Thereactor was purged first with nitrogen and then hydrogen, and thenpressurized with 50 psig (0.4 MPa) hydrogen and stirred at 600 rpm whileheating the reaction mixture to 150° C. On reaching this reactiontemperature, the reactor was further pressurized to 1000 psig (7.0 MPa)with hydrogen and maintained at this pressure by adding additionalhydrogen as required for the duration of the reaction.

After 6 hours at these conditions, the reactor was cooled and vented,and the liquid reaction mixture was recovered for product isolation. Thecrude mixture was filtered through a glass frit via aspirator vacuum toremove the catalyst, followed by removal of byproduct ethanol andunreacted N,N-dimethylethylenediamine in vacuo. The remaining contentswere fractionally distilled with a 20-cm Vigreaux column under highvacuum (˜0.05 mmHg) to give 136.5 g water-white product at 85° C. in 77%isolated yield. Product purity was >99% as determined by GC/MS (HP-6890equipped with MSD).

Example 2 Synthesis of1-(N,N,N-dimethyl(ethylethoxy)aminoethyl)-5-methyl-pyrrolid in-2-onebis(trifluoromethane)sulfonamide ([MeDMEEAP][TF₂N])

1-(N,N,N-dimethyl(ethylethoxy)aminoethyl)-5-methyl-pyr rolidin-2-onebis(trifluoromethane)sulfonamide ([MeDMEEAP][TF₂N]), C₁₅H₂₇N₃O₆ F₆S₂,with a molecular weight of 523.51 g mol⁻¹ and structure as shown inFormula 5, was prepared as follows:

1-(2-(dimethylamino)ethyl)-5-methylpyrrolidin-2-one (MeDMAP), C₉H₁₈N₂O,with a molecular weight of 170.25 g mol⁻¹ and a purity of >99% by GC/MS,was used as prepared in Example 1. To a two-neck 100-mL round bottomflask equipped with a nitrogen-purged reflux condenser was added 24.27 g(0.143 moles) MeDMAP, 30.40 g (0.280 moles) 2-chloroethyl ethyl ether,and 17.81 g acetonitrile as reaction solvent. The condenser was cooledby a recirculating bath filled with a 50 wt % mixture of water andpropylene glycol maintained at approximately 16° C. The reaction mixturewas heated to 85° C. under reflux and nitrogen purge with atemperature-controlled oil bath. This reaction temperature wasmaintained for 120 hrs, at which time the conversion of the MeDMAP wasabout 94.4% by ¹H NMR spectroscopy.

The reaction mixture was then thermally quenched and extracted withmultiple diethyl ether and ethyl acetate washes to remove startingmaterials and to purify the intermediate product. The solvents wereremoved in vacuo with a rotary evaporator, and the intermediate productwas then dried under high vacuum (approximately 10⁻⁶ torr) using aturbomolecular pump and heating the material to about 70-80° C.overnight. The resulting intermediate product of this reaction,1-(N,N,N-dimethyl(ethylethoxy)aminoethyl)-5-methyl-pyrrolid in-2-onechloride ([MeDMEEAP][Cl]), C₁₃H₂₇N₂O₂Cl, with a molecular weight of278.82 g mol⁻¹, was determined to have a final purity of about 95.1% by¹H NMR spectroscopy.

In a 500-mL round bottom flask, 11.50 g (0.0413 mol) of this[MeDMEEAP][Cl] intermediate was dissolved in approximately 150 mL ofpurified water, chilled in an ice bath, and then mixed with 12.81 g(0.0456 mol) bis(trifluoromethane)sulfonimide dissolved in approximately150 mL water. After stirring the reaction solution overnight at roomtemperature, the resulting IL was purified by extracting the resultinghydrochloric acid and the excess bis(trifluoromethane)sulfonamide withmultiple water washes of about 15 mL each while keeping the IL productpartitioned in an organic phase with dichloromethane. Water was removedfrom the filtrate in vacuo with a rotary evaporator, then the productwas dried under high vacuum (approximately 10⁻⁵ torr) using aturbomolecular pump and heating the material to about 70° C. overnight.The resulting [MeDMEEAP][Tf₂N] product purity was estimated to be about95% by ¹H NMR spectroscopy.

Example 3 Synthesis of1-(N,N,N-dimethyl(ethylethoxy)aminoethyl)-5-methyl-pyrrolid in-2-onehexafluoropropanesulfonate ([MeDMEEAP][HFPS])

1-(N,N,N-dimethyl(ethylethoxy)aminoethyl)-5-methyl-pyr rolidin-2-onehexafluoropropanesulfonate ([MeDMEEAP][HFPS]), C₁₅H₂₆N₂O₅F₆S, with amolecular weight of 460.43 g mol⁻¹ and structure as shown in Formula 6,was prepared as follows:

1-(N,N,N-dimethyl(ethylethoxy)aminoethyl)-5-methyl-pyr rolidin-2-onechloride ([MeDMEEAP][Cl]), C₁₃H₂₇N₂O₂Cl, with a molecular weight of278.82 g mol⁻¹ and final purity of about 95.1% by ¹H NMR spectroscopy,was used as prepared in Example 5. In a 500-mL round bottom flask, 11.28g (0.0405 mol) of this 95% [MeDMEEAP][Cl] intermediate was dissolved inapproximately 100 mL of acetone, and then 10.51 g (0.0389 mol) potassiumhexafluoropropanesulfonate dissolved in approximately 50 mL of acetonewas slowly added. After stirring the reaction solution overnight at roomtemperature, the IL product was filtered through a fritted funnel toremove the resulting potassium chloride crystals. The filtrate wasallowed to set for about a week, and additional potassium chloridecrystals formed and were removed by filtration through a fritted funnel.The solvent was removed in vacuo with a rotary evaporator, and then theproduct was dried under high vacuum (approximately 10⁻⁵ torr) using aturbomolecular pump and heating the material to about 70° C. overnight.The final purity of the resulting [MeDMEEAP][HFPS]product wasapproximately 98% by ¹H NMR spectroscopy.

Example 4 Synthesis of1-(N,N,N-dimethyl(methylethoxy)aminoethyl)-5-methylpyrrolid in-2-onebis(trifluoromethane)sulfonamide ([MeDMMEAP][TF₂N])

1-(N,N,N-dimethyl(methylethoxy)aminoethyl)-5-methylpyr rolidin-2-onebis(trifluoromethane)sulfonamide ([MeDMMEAP][TF₂N]), C₁₄H₂₅N₃O₆F₆S₂,with a molecular weight of 509.49 g mol⁻¹ and structure as shown inFormula 7, was prepared as follows:

1-(2-(dimethylamino)ethyl)-5-methylpyrrolidin-2-one (MeDMAP), C₉H₁₈N₂O,with a molecular weight of 170.25 g mol⁻¹ and a purity of >99% by GC/MS,was used as prepared in Example 1. To a two-neck 100-mL round bottomflask equipped with a nitrogen-purged reflux condenser was added 20.88 g(0.123 moles) MeDMAP, 23.93 g (0.253 moles) 2-chloroethyl methyl ether,and 25.03 g acetonitrile as reaction solvent. The condenser was cooledby a recirculating bath filled with a 50 wt % mixture of water andpropylene glycol maintained at approximately 16° C. The reaction mixturewas heated to 85° C. under reflux and nitrogen purge with atemperature-controlled oil bath. This reaction temperature wasmaintained for 116 hrs, at which time the conversion of the MeDMAP wasabout 95.5% by ¹H NMR spectroscopy.

The reaction mixture was thermally quenched at about 120 hrs reactiontime. The intermediate product of this reaction,1-(N,N,N-dimethyl(methylethoxy)aminoethyl)-5-methylpyrrolid in-2-onechloride ([MeDMMEAP][Cl]), C₁₂H₂₅N₂O₂Cl, with a molecular weight of264.79 g mol⁻¹, was then extracted with multiple diethyl etherextractions (approximately 220 mL in 30-40 mL increments) to removestarting materials. The reaction mixture was then dissolved indichloromethane and filtered through a column packed with acidic andneutral alumina. The solvent was removed from the filtrate in vacuo witha rotary evaporator, and the product was then dried under high vacuum(approximately 10⁻⁶ torr) using a turbomolecular pump and heating thematerial to about 70-80° C. overnight. The final purity of this chloridesalt intermediate was approximately 96.4% by ¹H NMR spectroscopy.

In a 500-mL round bottom flask, 13.07 g (0.0494 mol) of this[MeDMMEAP][Cl] intermediate was dissolved in approximately 150 mL ofpurified water, chilled in an ice bath, and then mixed with 15.54 g(0.0553 mol) bis(trifluoromethane)sulfonimide dissolved in approximately150 mL water. After stirring the reaction solution overnight at roomtemperature, the resulting IL was purified by extracting the resultinghydrochloric acid and the excess bis(trifluoromethane)sulfonamide withmultiple water washes of about 15 mL each while keeping the IL productpartitioned in an organic phase with dichloromethane. Water was removedfrom the filtrate in vacuo with a rotary evaporator, then the productwas dried under high vacuum (approximately 10⁻⁵ torr) using aturbomolecular pump and heating the material to about 70° C. overnight.The resulting [MeDMMEAP][Tf₂N] product purity was estimated to be about96% by ¹H NMR spectroscopy.

Example 5 Synthesis of1-(N,N,N-dimethyl(methylethoxy)aminoethyl)-5-methylpyrrolid in-2-onehexafluoropropanesulfonate ([MeDMMEAP][HFPS])

1-(N,N,N-dimethyl(methylethoxy)aminoethyl)-5-methylpyr rolidin-2-onehexafluoropropanesulfonate ([MeDMMEAP][HFPS]), C₁₅H₂₆N₂O₅F₆S, with amolecular weight of 460.43 g mol⁻¹ and structure as shown in Formula 8,was prepared as follows:

1-(N,N,N-dimethyl(methylethoxy)aminoethyl)-5-methylpyr rolidin-2-onechloride ([MeDMMEAP][Cl]), C₁₂H₂₅N₂O₂Cl, with a molecular weight of264.79 g mol⁻¹ and a purity of about 96.4% by ¹H NMR spectroscopy wasused as prepared in Example 4.

In a 500-mL round bottom flask, 12.94 g (0.0489 mol) of this 96.4%[MeDMMEAP][Cl] intermediate was dissolved in approximately 100 mL ofacetone, and then 14.59 g (0.0540 mol) potassiumhexafluoropropanesulfonate was slowly added to this mixture. Afterstirring the reaction solution overnight at room temperature, the ILproduct was filtered through a fritted funnel containing Celite® toremove the resulting potassium chloride crystals. The solvent wasremoved in vacuo with a rotary evaporator, and then the[MeDMMEAP][HFPS]product was dissolved in dichloromethane and filteredthrough a column containing basic and neutral alumina. Methanol anddichloromethane were used to recover the product from the column. Thesolvent was removed in vacuo with a rotary evaporator, and then theproduct was dried under high vacuum (approximately 10⁻⁵ torr) using aturbomolecular pump and heating the material to about 70° C. overnight.The final purity of the resulting [MeDMMEAP][HFPS] product wasapproximately 96% by ¹H NMR spectroscopy.

Example 6 Synthesis of1-(N,N,N-dimethyl(hyrdoxyethyl)aminoethyl)-5-methylpyrrolid in-2-onebis(trifluoromethane)sulfonamide ([MeDMHEAP][TF₂N])

1-(N,N,N-dimethyl(hyrdoxyethyl)aminoethyl)-5-methylpyr rolidin-2-onebis(trifluoromethane)sulfonamide ([MeDMHEAP][TF₂N]), C₁₃H₂₃N₃O₆F₆S₂,with a molecular weight of 495.46 g mol⁻¹ and structure as shown inFormula 9, was prepared as follows:

1-(2-(dimethylamino)ethyl)-5-methylpyrrolidin-2-one (MeDMAP), C₉H₁₈N₂O,with a molecular weight of 170.25 g mol⁻¹ and a purity of >99% by GC/MS,was used as prepared in Example 1.

To a two-neck 100-mL round bottom flask equipped with a nitrogen-purgedreflux condenser was added 16.97 g (0.0997 moles) MeDMAP, 15.92 g (0.198moles) 2-chloroethanol, and 18.63 g acetonitrile as reaction solvent.The condenser was cooled by a recirculating bath filled with a 50 wt %mixture of water and propylene glycol maintained at approximately 16° C.The reaction mixture was heated to 85° C. under reflux and nitrogenpurge with a temperature-controlled oil bath. This reaction temperaturewas maintained for 100 hrs, and then the reaction mixture was thermallyquenched and dried under high vacuum (approximately 10⁻⁵ torr) using aturbomolecular pump and heating the material to about 70° C. overnight.The intermediate product of this reaction,1-(N,N,N-dimethyl(hyrdoxyethyl)aminoethyl)-5-methylpyrrolid in-2-onechloride ([MeDMHEAP][Cl]), C₁₁H₂₃N₂O₂Cl, with a molecular weight of250.77 g mol⁻¹, was determined to have a final purity of 95.6% by ¹H NMRspectroscopy.

In a 500-mL round bottom flask, 13.75 g (0.0548 mol) of this[MeDMMEAP][Cl] intermediate was dissolved in approximately 150 mL ofpurified water, chilled in an ice bath, and then mixed with 15.95 g(0.0567 mol) bis(trifluoromethane)sulfonimide dissolved in approximately150 mL water. After stirring the reaction solution overnight at roomtemperature, the resulting IL was purified by extracting the resultinghydrochloric acid and the excess bis(trifluoromethane)sulfonamide withmultiple water washes of about 15 ml each while keeping the IL productpartitioned in an organic phase with dichloromethane. Water was removedfrom the filtrate in vacuo with a rotary evaporator, then the productwas dried under high vacuum (approximately 10⁻⁵ torr) using aturbomolecular pump and heating the material to about 70° C. overnight.The resulting [MeDMMEAP][Tf₂N] product purity was estimated to be 97.8%by ¹H NMR spectroscopy.

Example 7 1-(N,N,N-dimethyl(hyrdoxyethyl)aminoethyl)-5-methylpyrrolidin-2-one levulinate [MeDMHEAP][Lev])

1-(N,N,N-dimethyl(hyrdoxyethyl)aminoethyl)-5-methylpyr rolidin-2-onelevulinate ([MeDMHEAP][Lev]), C₁₆H₃₀N₂O₅, with a molecular weight of330.42 g mol⁻¹ and structure as shown in Formula 10, was prepared asfollows:

1-(N,N,N-dimethyl(hyrdoxyethyl)aminoethyl)-5-methylpyr rolidin-2-onechloride ([MeDMHEAP][Cl]), C₁₁H₂₃N₂O₂Cl, with a molecular weight of250.77 g mol⁻¹ and final purity of 95.6%, was prepared as described inExample 5.

In a 500-mL Erlenmeyer flask, 12.550 (0.0500 mol) of this [MeDMHEAP][Cl]intermediate dissolved in approximately 150 mL of purified water wascombined with a slurry of 5.794 g (0.0250 mol) silver (I) oxide and6.433 g (0.0554 mol) levulinic acid in approximately 200 mL of purifiedwater. After stirring overnight at room temperature, the reactionmixture was filtered through a fritted funnel containing Celite® toremove the silver chloride product and residual silver (I) oxide. Waterwas removed from the filtrate in vacuo with a rotary evaporator, andthen the product was twice dissolved in methanol, filtered through afritted funnel containing Celite® to remove residual silver chloride andsilver (I) oxide, and then evaporated in vacuo with a rotary evaporatorto remove the methanol solvent. The product was then dried under highvacuum (approximately 10⁻⁵ torr) using a turbomolecular pump and heatingthe material to about 70° C. for two days. The resulting[MeDMHEAP][Lev]product was 98.9% purity by ¹H NMR spectroscopy.

Where a range of numerical values is recited or established herein, therange includes the endpoints thereof and all the individual integers andfractions within the range, and also includes each of the narrowerranges therein formed by all the various possible combinations of thoseendpoints and internal integers and fractions to form subgroups of thelarger group of values within the stated range to the same extent as ifeach of those narrower ranges was explicitly recited. Where a range ofnumerical values is stated herein as being greater than a stated value,the range is nevertheless finite and is bounded on its upper end by avalue that is operable within the context of the invention as describedherein. Where a range of numerical values is stated herein as being lessthan a stated value, the range is nevertheless bounded on its lower endby a non-zero value.

In this specification, unless explicitly stated otherwise or indicatedto the contrary by the context of usage, amounts, sizes, ranges,formulations, parameters, and other quantities and characteristicsrecited herein, particularly when modified by the term “about”, may butneed not be exact, and may also be approximate and/or larger or smaller(as desired) than stated, reflecting tolerances, conversion factors,rounding off, measurement error and the like, as well as the inclusionwithin a stated value of those values outside it that have, within thecontext of this invention, functional and/or operable equivalence to thestated value.

What is claimed is:
 1. A compound represented by the structure of thefollowing Formula 1:

wherein (a) Z is —(CH₂)_(n)—, wherein n is an integer from 2 to 12; (b)R² are R³ are each independently H or a C₁ to C₆ straight-chain orbranched alkyl group; (c) R⁴ is —[(CH₂)_(p)—X]_(q)—(CH₂)_(r)—Y—R⁶wherein X and Y are each independently O, r and p are each independentlyan integer from 1 to 4, q is an integer from 0 to 8, and R⁶ is H or a C₁to C₆ straight-chain or branched alkyl group; and (d) A⁻ is an anionselected from the group consisting of levulinate, [BF₄]⁻, [PF₆]⁻,[SbF₆]⁻, [CH₃CO₂]⁻, [HSO₄]⁻, [CF₃SO₃]⁻, [HCF₂CF₂SO₃]⁻, [CF₃HFCCF₂SO₃]⁻,[CF₃—O—CFHCF₂SO₃]⁻, [CF₃CF₂OCFHCF₂SO₃]⁻, [CF₃CF₂CF₂OCFHCF₂SO₃]⁻,[HCClFCF₂SO₃]⁻, [(CF₃SO₂)₂N]⁻, [AlCl₄]⁻, [CF₃CO₂]⁻, [NO₃]⁻, [SO₄]²⁻,Cl⁻, Br⁻, I⁻, and F⁻.
 2. A compound according to claim 1 wherein Z is—(CH₂)_(n)—, wherein n is an integer from 2 to
 6. 3. A compoundaccording to claim 1 wherein n is
 2. 4. A compound according to claim 1wherein q is 0 to
 4. 5. A compound according to claim 1 wherein q is 0.6. A compound according to claim 1 wherein r and p are 2 to
 4. 7. Acompound according to claim 1 wherein r and p are
 2. 8. A compoundaccording to claim 1 wherein R⁶ is H.
 9. A compound according to claim 1wherein R² and R³ taken independently are H, —CH₃, —CH₂CH₃, and—CH₂CH₂CH₃.
 10. A compound according to claim 1 wherein R² and R³ are—CH₃.
 11. A compound according to claim 1 wherein R⁴ is—(CH₂)₂—O—(C₂H₅), —(CH₂)₂—O—(CH₃), or —(CH₂)₂—OH.
 12. A compoundaccording to claim 1 wherein A⁻ is levulinate, [CF₃HFCCF₂SO₃]⁻, or[(CF₃SO₂)₂N]⁻.